Compositions stabilized with substituted alkoxybenzylhydroxylamines

ABSTRACT

Substituted alkoxybenzylhydroxylamines of the formula ##STR1## are effective in stabilizing organic materials against oxidative, thermal and actinic degradation, said derivatives being particularly effective as color improvers and process stabilizers in organic materials containing phenolic antioxidants; and certain of said derivatives as new compounds.

Organic polymeric materials such as plastics and resins are subject tothermal, oxidative and photodegradation. A great variety of stabilizersare known in the art for stabilizing a diversity of substrates. Theireffectiveness varies depending upon the causes of degradation and thesubstrate stabilized. In general, it is difficult to predict whichstabilizer will be most effective and most economical for any one areaof application. For example, stabilizer effectiveness in reducingvolatility may depend upon preventing bond scission in the substratemolecule. Limiting embrittlement and retaining elasticity in a polymeror rubber may require prevention of excessive crosslinking and/or chainscission. Prevention of discoloration may require inhibiting reactionswhich yield new chromophores or color bodies in the substrate orstabilizer. Problems of process stability and incompatibility must alsobe considered.

Various organic hydroxylamine compounds are generally known and some arecommercially available. A number of patents disclosenitrogen-substituted hydroxylamines as antioxidant stabilizers forvarious substrates including polyolefins, polyesters and polyurethanes.U.S. Pat. Nos. 3,432,578, 3,644,278, 3,778,464, 3,408,422, 3,926,909,4,316,996 and 4,386,224 are representative of such patents whichbasically disclose N,N-dialkyl-, N,N-diaryl and N,N-diaralkylhydroxylamine compounds and their color improvement and colorstabilizing activity. For example, U.S. Pat. No. 3,926,909 disclosesbis(4-methoxybenzyl)hydroxylamine, bis(4-ethoxybenzyl)hydroxylamine,bis(4-phenoxybenzyl)hydroxylamine and bis(4-butoxyphenyl)hydroxylamineas stabilizers for protecting spandex and other forms of polyurethanes.

It has now been determined that the compositions of this inventionexhibit a variety of desirable properties stemming from the presencetherein of the indicated hydroxylamine derivatives. Thus, the compoundsserve to protect various substrates such as polyolefins, elastomers andlubricating oils against the adverse effects of oxidative and thermaldegradation. These compounds are of higher molecular weight and thusmore extraction resistant from the substrate. They are most effective ascolor improvers and process stabilizers in polyolefin compositions whichmay contain metal salts of fatty acids and which also contain a phenolicantioxidant. Thus, they serve to substantially reduce color formationresulting from the presence of the phenolic antioxidant and/or from theprocessing conditions as well as to directly protect the polymer fromsaid processing conditions. They also prevent the discoloration ofpolyolefin compositions containing hindered amine light stabilizers orcombinations of phenolic antioxidants and organic phosphites. Inaddition, the gas fading that may be experienced upon exposure to thecombustion products of natural gas is also significantly reduced.

It is a primary object of this invention to provide compositions oforganic materials stabilized against oxidative, thermal and actinicdegradation by the presence therein of a class of substitutedalkoxybenzylhydroxylamines.

It is a further object to provide such compositions which also containphenolic antioxidants wherein said derivatives substantially reducecolor formation resulting from the presence of said phenols.

It is still a further object to provide a specific class of novelsubstituted alkoxybenzylhydroxylamine derivatives which likewise exhibita broad range of improved stabilization performance characteristics.

Various other objects and advantages of this invention will becomeevident from the following description thereof.

The stabilizing compounds utilized in the compositions of this inventioncorrespond to the formula ##STR2## wherein R₁ is hydrogen, alkyl of 1 to36 carbon atoms, cycloalkyl of 5 to 12 carbon atoms, aralkyl of 7 to 9carbon atoms or said aralkyl substituted by alkyl of 1 to 36 carbonatoms or --OR₃, wherein R₃ is hydrogen, alkyl of 1 to 36 carbon atoms,cycloalkyl of 5 to 12 carbon atoms, aralkyl of 7 to 9 carbon atoms orsaid aralkyl substituted by alkyl of 1 to 36 carbon atoms;

n is 1-4;

R₂, when n is 1, is hydrogen, alkyl of 1 to 36 carbon atoms, cycloalkylof 5 to 12 carbon atoms, aralkyl of 7 to 9 carbon atoms, or said aralkylsubstituted by alkyl of 1 to 36 carbon atoms;

R₂, when n is 2, is alkylene of 2 to 12 carbon atoms, alkylidene of 2 to6 carbon atoms, cycloalkylene of 6 to 10 carbon atoms, arylene of 6 to10 atoms or alkylenearylenealkylene of 8 to 10 carbon atoms;

R₂, when n is 3, is alkanetriyl of 3 to 6 carbon atoms; and

R₂, when n is 4, is alkanetetrayl of 4 to 6 carbon atoms.

The R₁ group is preferably straight-chain or branched alkyl with 1 to 18carbon atoms such as methyl, ethyl, n-propyl, n-butyl, tert-butyl,n-pentyl, n-octyl, 2-ethylhexyl, decyl, dodecyl and octadecyl;cyclopentyl and cyclohexyl; benzyl, α-methylbenzyl andα,α-dimethylbenzyl; and the substituted benzyloxy group wherein R₃ ispreferably the same as the preferred R₁ groups absent benzyloxy.

R₂, when n is 1, is preferably similar to the list of preferred R₁groups absent benzyloxy. It is further preferred that R₂ is identical toR₃ when n is 1 and R₁ is substituted benzyloxy.

R₂, when n is 2, is preferably alkylene of 2 to 12 carbon atoms,including ethylene, hexamethylene and octamethylene, ethylidene,cyclohexylene, phenylene and xylylene.

R₂, when n is 3, is preferably glyceryl and trimethylyl propane, whileR₂, when n is 4, is preferably pentaerythrityl.

The primary method for preparing the derivatives involves reacting theappropriately unsubstituted or substituted hydroxyamine hydrochloridewith an appropriately substituted benzyl bromide (BrCH₂ C₆ H₄ O)_(n) R₂in a solvent to yield the desired product. The solvent can be anaromatic hydrocarbon such as benzene, toluene, xylene, and the like, aheterocyclic ether such as tetrahydrofuran, or preferably a solvent suchas dimethylformamide. The reaction temperature ranges from 25° to 100°C. It is preferred in this reaction approach to conduct the reaction inthe presence of an acid acceptor such as sodium carbonate. The startingmaterials are items of commerce or can be prepared by known methods.

The compounds utilized in the compositions of the present invention areparticularly effective in stabilizing organic materials subject tooxidative, thermal and actinic degradation, such as plastics, polymersand resins.

Substrates in which these compounds are particularly useful arepolyolefins such as polyethylene and polypropylene; polystyrene,including impact polystyrene, ABS resin, SBR, isoprene, as well asnatural rubber, polyesters including polyethylene terephthalate andpolybutylene terephthalate, including copolymers, and lubricating oilssuch as those derived from mineral oil.

In general polymers which can be stabilized include

1. Polymers of monoolefins and diolefins, for example polyethylene(which optionally can be crosslinked), polypropylene, polyisobutylene,polybutene-1, polymethylentene-1, polyisoprene or polybutadiene, as wellas polymers of cycloolefins, for instance of cyclopentene or norbornene.

2. Mixtures of the polymers mentioned under (1), for example mixtures ofpolypropylene with polyisobutylene.

3. Copolymers of monoolefins and diolefins with each other or with othervinyl monomers, such as, for example, ethylene/propylene,propylene/butene-1, propylene/isobutylene, ethylene/butene-1,propylene/butadiene, isobutylene/isoprene, ethylene/alkyl acrylates,ethylene/alkyl methacrylates, ethylene/vinyl acetate or ethylene/arylicacid copolymers and their salts (ionomers) and terpolymers of ethylenewith propylene and a diene, such as hexadiene, dicyclopentadiene orethylidene-norbornene.

4. Polystyrene, poly-(p-methylstyrene).

5. Copolymers of styrene or methylstyrene with dienes or acrylicderivatives, such as, for example, styrene/butadiene,styrene/acrylonitrile, styrene/ethyl methacrylate,styrene/butadiene/ethyl acrylate, styrene/acrylonitrile/methyl acrylate;mixtures of high impact strength from styrene copolymers and anotherpolymer, such as, for example, from a polyacrylate, a diene polymer oran ethylene/propylene/diene terpolymer; and block polymers of styrene,such as, for example, styrene/butadiene/styrene,styrene/isoprene/styrene, styrene/ethylene/butylene/styrene orstyrene/ethylene/propylene/styrene.

6. Graft copolymers of styrene, such as, for example, styrene onpolybutadiene, styrene and acrylonitrile on polybutadiene, styrene andalkyl acrylates or methacrylates on polybutadiene, styrene andacrylonitrile on ethylene/propylene/diene terpolymers, styrene andacrylonitrile on polyacrylates or polymethacrylates, styrene andacrylonitrile on acrylate/butadiene copolymers, as well as mixturesthereof with the copolymers listed under (5), for instance the copolymermixtures known as ABS-, MBS-, ASA- or AES-polymers.

7. Halogen-containing polymers, such as polychloroprene, chlorinatedrubbers, chlorinated or sulfochlorinated polyethylene, epichlorohydrinhomo- and copolymers, polymers from halogen-containing vinyl compounds,as for example, polyvinylchloride, polyvinylidene chloride, polyvinylfluoride, polyvinylidene fluoride, as well as copolymers thereof, as forexample, vinyl chloride/vinylidene chloride, vinyl chloride/vinylacetate or vinylidene chloride/vinyl acetate copolymers.

8. Polymers which are derived from α,β-unsaturated acids and derivativesthereof, such as polyacrylates and polymethacrylates, polyacrylamide andpolyacrylonitrile.

9. Copolymers from the monomers mentioned under (8) with each other orwith other unsaturated monomers, such as, for instance,acrylonitrile/butadiene, acrylonitrile/alkyl acrylate,acrylonitrile/alkoxyalkyl acrylate or acryloacrylate, nitrile/vinylhalogenide copolymers or acrylonitrile/alkyl methacrylate/butadieneterpolymers.

10. Polymers which are derived from unsaturated alcohols and amines, oracyl derivatives thereof or acetals thereof, such as polyvinyl alcohol,polyvinyl acetate, polyvinyl stearate, polyvinyl benzoate, polyvinylmaleate, polyvinylbutyral, polyallyl phthalate or polyallyl-melamine.

11. Homopolymers and copolymers of cyclic ethers, such as polyalkyleneglycols, polyethylene oxide, polypropylene oxide or copolymers thereofwith bis-glycidyl ethers.

12. Polyacetals, such as polyoxymethylene and those polyoxymethyleneswhich contain ethylene oxide as comonomer.

13. Polyphenylene oxides and sulfides, and mixtures of polyphenyleneoxides with polystyrene.

14. Polyurethanes which are derived from polyethers, polyesters orpolybutadiens with terminal hydroxyl groups on the one side andaliphatic or aromatic polyisocyanates on the other side, as well asprecursors thereof (polyisocyanates, polyols or prepolymers).

15. Polyamides and copolyamides which are derived from diamines anddicarboxylic acids and/or from aminocarboxylic acids or thecorresponding lactams, such as polyamide 4, polyamide 6, polyamide 6/6,polyamide 6/10, polyamide 11, polyamide 12,poly-2,4,4-trimethylhexamethylene terephthalamide or poly-m-phenyleneisophthalamide, as well as copolymers thereof with polyethers, such asfor instance with polyethylene glycol, polypropylene glycol orpolytetramethylene glycols.

16. Polyureas, polyimides and polyamide-imides.

17. Polyesters which are derived from dicarboxylic acids and diolsand/or from hydroxycarboxylic acids or the corresponding lactones, suchas polyethylene terephthalate, polybutylene terephthalate,poly-1,4-dimethylol-cyclohexane terephthalate,poly-[2,2-(4-hydroxyphenyl)-propane]terephthalate andpolyhydroxybenzoates as well as blockcopolyether-esters derived frompolyethers having hydroxyl end groups.

18. Polycarbonates.

19. Polysulfones, polyethersulfones and polyetherketones.

20. Crosslinked polymers which are derived from aldehydes on the onehand and phenols, ureas and melamines on the other hand, such asphenol/formaldehyde resins, urea/formaldehyde resins andmelamine/formaldehyde resins.

21. Drying and non-drying alkyd resins.

22. Unsaturated polyester resins which are derived from copolyesters ofsaturated and unsaturated dicarboxylic acids with polyhydric alcoholsand vinyl compounds as crosslinking agents, and also halogen-containingmodifications thereof of low flammability.

23. Thermosetting acrylic resins, derived from substituted acrylicesters, such as epoxy-acrylates, urethane-acrylates or polyesteracrylates.

24. Alkyd resins, polyester resins or acrylate resins in admixture withmelamine resins, urea resins, polyisocyanates or epoxide resins ascrosslinking agents.

25. Crosslinked epoxide resins which are derived from polyepoxides, forexample from bis-glycidyl ethers or from cycloaliphatic diepoxides.

26. Natural polymers, such as cellulose, rubber, gelatin and derivativesthereof which are chemically modified in a polymer homologous manner,such as cellulose acetates, cellulose propionates and cellulosebutyrates, or the cellulose ethers, such as methylcellulose.

27. Mixtures of polymers as mentioned above, for example PP/EPDM,Polyamide 6/EPDM or ABS, PVC/EVA, PVC/ABS, PVC/MBS, PC/ABS, PBTP/ABS.

28. Naturally occuring and synthetic organic materials which are puremonomeric compounds or mixtures of such compounds, for example mineraloils, animal and vegetable fats, oil and waxes, or oils, fats and waxesbased on synthetic esters (e.g. phthalates, adipates, phosphates ortrimellitates) and also mixtures of synthetic esters with mineral oilsin any weight ratios, which materials may be used as plasticizers forpolymers or as textile spinning oils, as well as aqueous emulsions ofsuch materials.

29. Aqueous emulsions of natural or synthetic rubber, e.g. natural latexor latices of carboxylated styrene/butadiene copolymers.

In general, the compounds of the present invention are employed in fromabout 0.01 to about 5% by weight of the stabilized composition, althoughthis will vary with the particular substrate and application. Anadvantageous range is from about 0.5 to about 2%, and especially 0.1 toabout 1%.

The stabilizers of the instant invention may readily be incorporatedinto the organic polymers by conventional techniques, at any convenientstage prior to the manufacture of shaped articles therefrom. Forexample, the stabilizer may be mixed with the polymer in dry powderform, or a suspension or emulsion of the stabilizer may be mixed with asolution, suspension, or emulsion of the polymer. The resultingstabilized polymer compositions of the invention may optionally alsocontain various conventional additives, such as the following.

1 Antioxidants

1.1. Alkylated monophenols, for example,

2,6-di-tert.butyl-4-methylphenol

2-tert.butyl-4,6-dimethylphenol

2,6-di-tert.butyl-4-ethylphenol

2,6-di-tert.butyl-4-n-butylphenol

2,6-di-tert.butyl-4-i-butylphenol

2,6-di-cyclopentyl-4-methylphenol

2-(α-methylcyclohexyl)-4,6-dimethylphenol

2,6-di-octadecyl-4-methylphenol

2,4,6-tri-cyclohexylphenol

2,6-di-tert.butyl-4-methoxymethylphenol

1.2. Alkylated hydroquinones, for example,

2,6-di-tert.butyl-4-methoxyphenol

2,5-di-tert.butyl-hydroquinone

2,5-di-tert.amyl-hydroquinone

2,6-diphenyl-4-octadecyloxyphenol

1.3. Hydroxylated thiodiphenyl ethers, for example

2,2'-thio-bis-(6-tert.butyl-4-methylphenol)

2,2'-thio-bis-(4-octylphenol)

4,4'-thio-bis-(6-tert.butyl-3-methylphenol)

4,4'-thio-bis-(6-tert.butyl-2-methylphenol)

1.4. Alkylidene-bisphenols, for example,

2,2'-methylene-bis-(6-tert.butyl-4-methylphenol)

2,2'-methylene-bis-(6-tert.butyl-4-ethylphenol)

2,2'-methylene-bis-[4-methyl-6-(α-methylcyclohexyl)-phenol]

2,2'-methylene-bis-(4-methyl-6-cyclohexylphenol)

2,2'-methylene-bis-(6-nonyl-4-methylphenol)

2,2'-methylene-bis-[6-(α-methylbenzyl)-4-nonylphenol]

2,2'-methylene-bis-[6-(α,α-dimethylbenzyl)-4-nonylphenol]

2,2'-methylene-bis-(4,6-di-tert.butylphenol)

2,2'-ethylidene-bis-(4,6-di-tert.butylphenol)

2,2'-ethylidene-bis-(6-tert.butyl-4-isobutylphenol)

4,4'-methylene-bis-(2,6-di-tert.butylphenol)

4,4'-methylene-bis-(6-tert.butyl-2-methylphenol)

1,1-bis-(5-tert.butyl-4-hydroxy-2-methylphenyl-butane

2,6-di-(3-tert.butyl-5-methyl-2-hydroxybenzyl)-4-methylphenol

1,1,3-tris-(5-tert.butyl-4-hydroxy-2-methylphenyl)-butane

1,1-bis-(5-tert.butyl-4-hydroxy-2-methylphenyl)-3-n-dodecylmercaptobutane

ethylenglycol-bis-[3,3-bis-(3'-tert.butyl-4'-hydroxyphenyl)-butyrate]

di-(3-tert.butyl-4-hydroxy-5-methylphenyl)-dicyclopentadiene

di-[2-(3'-tert.butyl-2'-hydroxy-5'-methyl-benzyl)-6-tert.butyl-4-methylphenyl]-terephthalate.

1.5. Benzyl compounds, for example,

1,3,5-tri-(3,5-di-tert.butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene-di-(3,5-di-tert.butyl-4-hydroxybenzyl)sulfide

3,5-di-tert.butyl-4-hydroxybenzyl-mercapto-acetic acid isooctyl ester

bis-(4-tert.butyl-3-hydroxy-2,6-dimethylbenzyl)dithiolterephthalate

1,3,5-tris-(3,5-di-tert.butyl-4-hydroxybenzyl)-isocyanurate

1,3,5-tris-(4-tert.butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurate

3,5-di-tert.butyl-4-hydroxybenzyl-phosphoric acid-dioctadecyl ester

3,5-di-tert.butyl-4-hydroxybenzyl-phosphoric acid-monoethyl ester,calcium-salt

1.6 Acylaminophenols, for example,

4-hydroxy-lauric acid anilide

4-hydroxy-stearic acid anilide

2,4-bis-octylmercapto-6-(3,5-tert.butyl-4-hydroxyanilino)s-triazine

octyl-N-(3,5-di-tert.butyl-4-hydrixphenyl)-carbamate

1.7. Esters of ? -(3,5-di-tert-butyl-4-hydroxphenyl)-propionic acid withmonohydric or polyhydric alcohols, for example,

    ______________________________________                                        methanol        diethyleneglycol                                              octadecanol     triethyleneglycol                                             1,6-hexanediol  pentaerythritol                                               neopentylglycol tris-hydroxyethyl isocyanurate                                thiodiethyleneglycol                                                                          di-hydroxyethyl oxalic acid                                                   diamide                                                       ______________________________________                                    

1.8. Esters of β -(5-tert-butyl-4-hydroxy-3-methylphenyl)-propionic acidwith monohydric or polyhydric alcohols, for example,

    ______________________________________                                        methanol        diethyleneglycol                                              octadecanol     triethyleneglycol                                             1,6-hexanediol  pentaerythritol                                               neopentylglycol tris-hydroxyethyl isocyanurate                                thiodiethyleneglycol                                                                          di-hydroxyethyl oxalic acid                                                   diamide                                                       ______________________________________                                    

1.9. Amides of β-(3,5-di-tert.butyl-4-hydroxyphenyl)-propionic acid forexample,

N,N'-di-(3,5-di-tert.butyl-4-hydroxyphenylpropionyl)-hexamethylenediamine

N,N'-di-(3,5-di-tert.butyl-4-hydroxyphenylpropionyl)-trimethylenediamine

N,N'-di-(3,5-di-tert.butyl-4-hydroxyphenylpropionyl)-hydrazine

2. UV absorbers and light stabilizers

2.1. 2-(2'-Hydroxyphenyl)-benzotriazoles, for example, the 5'-methyl-,3',5'-di-tert.butyl-, 5'-tert.butyl-, 5'-(1,1,3,3-tetramethylbutyl)-,5-chloro-3',5'-di-tert.butyl-, 5-chloro-3'-tert.butyl-5'-methyl-,3'-sec.butyl5'-tert.butyl-, 4'-octoxy, 3',5'-di-tert.amyl-,3',5'-bis-(α,α-dimethylbenzyl)-derivative.

2.2. 2-Hydroxy-benzophenones, for example, the 4-hydroxy-, 4-methoxy-,4-octoxy, 4-decyloxy-, 4-dodecyloxy-, 4-benzyloxy, 4,2',4'-trihydroxy-and 2'-hydroxy-4,4'-dimethoxy derivative.

2.3. Esters of optionally substituted benzoic acids for example, phenylsalicylate, 4-tert.butyl-phenylsalicylate, octylphenyl salicylate,dibenzoylresorcinol, bis-(4-tert.butylbenzoyl)-resorcinol,benzoylresorcinol, 3,5-di-tert.butyl-4-hydroxybenzoic acid2,4-di-tert.butyl-phenyl ester and 3,5-di-tert.-butyl-4-hydroxybenzoicacid hexadecyl ester.

2.4 Acrylates, for example, α-cyano-62 ,β-diphenylacrylic acid ethylester or isooctyl ester, α-carbomethoxy-cinnamic acid methyl ester,α-cyano-β-methyl-p-methoxy-cinnamic acid methyl ester or butyl ester,α-carbomethoxy-p-methoxycinnamic acid methyl ester,N-(β-carbomethoxy-β-cyanovinyl)-2-methyl-indoline.

2.5 Nickel compounds, for example, nickel complexes of2,2'-thio-bis-[4-(1,1,3,3-tetramethylbutyl)-phenol], such as the 1:1 or1:2 complex, optionally with additional ligands such as n-butylamine,triethanolamine or N-cyclohexyl-di-ethanolamine, nickeldibutyldithiocarbamate, nickel salts of4-hydroxy-3,5-di-tert.butylbenzylphosphonic acid monoalkyl esters, suchas of the methyl, ethyl or butyl ester, nickel complexes of ketoximessuch as of 2-hydroxy-4-methyl-phenyl undecyl ketoxime, nickel complexesof 1-phenyl-4-lauroyl-5-hydroxy-pyrazol, optionally with additionalligands.

2.6. Sterically hindered amines, for examplebis-(2,2,6,6-tetramethylpiperidyl)-sebacate,bis-(1,2,2,6,6-pentamethylpiperidyl)-sebacate,n-butyl-3,5-di-tert.butyl-4-hydroxybenzyl malonic acidbis-(1,2,2,6,6-pentamethylpiperidyl)ester, condensation product of1-hydroxyethyl-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinicacid, condensation product ofN,N'(2,2,6,6-tetramethylpiperidyl)-hexamethylenediamine and4-tert.octylamino-2,6-dichloro-1,3,5-s-triazine,tris(2,2,6,6-tetramethylpiperidyl)-nitrilotriacetate,tetrakis-(2,2,6,6-tetramethyl-4-piperidyl)-1,2,3,4-butanetetracarbonicacid, 1,1'(1,2-ethanediyl)-bis-(3,3,5,5-tetramethylpiperazinone).

2.7. Oxalic acid diamides, for example, 4,4'-di-octyloxyoxanilide,2,2'-di-octyloxy-5,5'-di-tert.butyl-oxanilide,2,2'-di-dodecyloxy-5,5'-di-tert.butyl-oxanilide,2-ethoxy-2'-ethyl-oxanilide, N,N'-bis (3-dimethylaminopropyl)oxalamide,2-ethoxy-5-tert.butyl-2'-ethyloxanilide and its mixture with2-ethoxy-2'-ethyl-5,4'-di-tert.butyloxanilide and mixtures of ortho- andpara-methoxy-as well as of o- and p-ethoxy-disubstituted oxanilides.

3. Metal deactivators, for example, N,N'-diphenyloxalic acid diamide,N-salicylal-N'-salicyloylhydrazine, N,N'-bis-salicyloylhydrazine,N,N'-bis-(3,5-di-tert.butyl-4-hydroxyphenylpropionyl)-hydrazine,3-salicyloylamino1,2,4-triazole, bis-benzylidene-oxalic aciddihydrazide.

4. Phosphites and phosphonites, for example, triphenyl phosphite,diphenylalkyl phosphites, phenyldialkyl phosphites,tri-(nonylphenyl)phosphite, trilauryl phosphite, trioctadecyl phosphite,di-stearyl-pentaerythritol diphosphite, tris-(2,4-di-tert.butylphenyl)phosphite, di-isodecylpentaerythritol diphosphite,di-(2,4-di-tert.butylphenyl)pentaerythritol diphosphite,tristearyl-sorbite triphosphite,tetrakis-(2,4-ditert.butylphenyl)-4,4'-diphenylylenediphosphonite.

5. Compounds which destroy peroxide, for example, esters ofβ-thiodipropionic acid, for example the lauryl, stearyl, myristyl ortridecyl esters, mercapto-benzimidazole or the zinc salt of2-mercaptobenzimidazole, zinc-dibutyl-dithiocarbamate,dioctadecyldisulfide,pentaerythritol-tetrakis(β-dodecylmercapto)-propionate.

6. Polyamide stabilizers, for example copper salts in combination withiodides and/or phosphorus compounds and salts of divalent manganese.

7. Basic co-stabilizers, for example, melamine, polyvinylpyrrolidone,dicyandiamide, triallyl cyanurate, urea derivatives, hydrazinederivatives, amines, polyamides, polyurethanes, alkali metal salts andalkaline earth metal salts of higher fatty acids for example Castearate, Zn stearate, Mg stearate, Na ricinoleate and K palmitate,antimony pyrocatecholate or zinc pyrocatecholate.

8. Nucleating agents, for example, 4-tert.butyl-benzoic acid, adipicacid, diphenylacetic acid.

9. Fillers and reinforcing agents, for example, calcium carbonate,silicates, glass fibers, asbestos, talc, kaolin, mica, barium sulfate,metal oxides and hydroxides, carbon black, graphite.

10. Other additives, for example, plasticizers, lubricants, emulsifiers,pigments, optical brighteners, flameproofing agents, anti-static agents,blowing agents and thiosynergists such as dilaurylthiodipropionate ordistearyl-thiodipropionate.

While the instant hydroxylamine derivatives can be beneficially used asstabilizers for a variety of substrates, particularly polyolefins, bothalone and in conjunction with other coadditives, the introduction of theinstant compounds into polyolefins, optionally containing various alkalimetal, alkaline earth metal and aluminum salts of higher fatty acids(see Additive #7 hereinabove), with hindered phenolic antioxidantsresults in enhanced and particularly salubrious protection to suchsubstrates in terms of reducing color formation stemming from thepresence of the phenols. Such phenolic antioxidants include n-octadecyl3,5-di-tert-butyl-4-hydroxyhydrocinnamate, neopentanetetrayltetrakis-(3,5-di-tert-butyl-4- hydroxyl-hydrocinnamate), di-n-octadecyl3,5-di-tert-butyl-4-hydroxybenzyl-phosphonate,1,3,5-tris(3,5-di-tert-butyl-4-hydroxy-benzyl)isocyanurate,thiodiethylene bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamate),1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl)benzene,3,6-di-oxaoctamethylenebis(3-methyl5-tert-butyl-4-hydroxyhydrocinnamate),2,6-di-tert-butyl-p-cresol,2,2'-ethylidene-bis(4,6-di-tert-butylphenol),1,3,5-tris(2,6-di-methyl-4-tert-butyl-3-hydroxybenzyl)isocyanurate,1,1,3-tris-(2-methyl-4-hydroxy-5-tert-butylphenyl)butane,1,3,5-tris-[2-(3,5-di-tert-butyl-4-hydroxy-hydrocinnamoyloxy)-ethyl]-isocyanurate, 3,5-di-(3,5-di-tert-butyl-4hydroxybenzyl)-mesitol,hexamethylene bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamate),1-(3,5-di-tert-butyl-4-hydroxyanilino)-3,5-di(octylthio)-s-triazine,N,N'-hexamethylene-bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamamide),calcium bis(ethyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate),ethylene bis[3,3-di(3-tert-butyl-4-hydroxyphenyl)butyrate], octyl3,5-di-tert-butyl4-hydroxybenzylmercaptoacetate,bis(3,5-di-tert-butyl4-hydroxyhydrocinnamoyl)hydrazide, andN,N'-bis-[2-(3,5-tert-butyl-4-hydroxyhydroxo-cinnamoyloxy)-ethyl]-oxamide,and preferably neopentanetetrayl tetrakis(3,5-di-tert-butyl-4-hydroxyhydrocinnamate), n-octadecyl3,5-di-tert-butyl-4-hydroxyhydrocinnamate,1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene,1,3,5-tris-(3,5-di-tert-butyl-4-hydroxy-benzyl) isocyanurate,2,6-di-tert-butyl-p-cresol or2,2'-ethylidene-bis(4,6-di-tert-butylphenol).

Likewise, the instant compounds prevent color formation when hinderedamine light stabilizers are present, such hindered amines includingbis(1,2,2,6,6-pentamethyl-4-piperidyl)-2-n-butyl-2-(3,5-di-tert-butyl-4-hydroxybenzyl)malonate; bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate;dimethylsuccinate polymer with4-hydroxy-2,2,6,6-tetramethyl-1-piperidinethanol; and polymer of2,4-dichloro-6-octylamino-s-triazine withN'-(2,2,6,6-tetramethyl-4-piperidyl)hexamethylene diamine.

As previously noted, certain hydroxylamine derivatives also form part ofthe instant invention. These derivatives correspond to the genericformula above wherein n is 2-4 (labelled m for these compounds). Thevarious substituent definitions, preferred substituents, preparativeprocedures and utility statements noted hereinabove equally apply tothese novel hydroxylamine derivatives.

The following examples illustrate the embodiments of this invention.Thus, they describe the preparation of various hydroxylaminederivatives, including those forming part of the invention, and ofstabilized compositions. In these examples, all parts given are byweight unless otherwise specified.

EXAMPLE I N, N-Bix-[p-methoxybenzyl]hydroxylamine

A stirred mixture of 4.66 g of hydroxylamine hydrochloride and 28.4 g ofsodium carbonate in 100 ml of dimethylformamide is admixed with asolution of 26.89 g of p-methoxybenzylbromide in 50 ml ofdimethylformamide. After stirring at room temperature for 15 hours, themixture is filtered and the filtrate concentrated under reduced pressureto leave a pale yellow residue. Trituration with ethanol affords theproduct as a white solid, mp 109°-11 °C.

Anal. calcd. for C₁₆ H₁₉ NO₃ : C, 70.3; H, 7.1; N, 5.1 Found: C, 70.4;H, 7.3; N, 5.3

EXAMPLE II N,N-Bis-[p-octadecyloxybenzyl]hydroxylamine

The procedure of Example I is repeated using 7.24 g of sodium carbonate,1.22 g of hydroxylamine hydrochloride and 15.38 g. ofp-octadecyloxybenzylbromide in dimethylformamide, to give the titlecompound as a white solid, M.P. 81°-83°C.

Anal. calcd. for C₅₀ H₈₇ NO₃ : C, 80.1; H, 11.7; N, 1.9 Found: C, 79.7;H, 12.0; N, 1.9

EXAMPLE III 1,12-Bis[4-(N-benzylhydroxyiminomethyl)phenoxy]dodecane

A mixture of 0.49 g of N-benzylhydroxylamine, 1.08 g of1,12-bis[4-(bromomethyl)phenoxy]dodecane and 0.42 g of sodium carbonatein 5 ml of dimethylformamide is stirred at room temperature for 8 hours.The reaction mixture is partitioned between ethyl acetate and water, andthe organic extract is washed with water, brine, dried (MgSO₄) andconcentrated under reduced pressure. The residue is purified by flashchromatography to afford the title compound as a white solid, mp105°-108°C.

Anal. Calcd. for C₄₀ H₅₂ N₂ O₄ : C, 76.9; H, 8.4; N, 4.5 Found: C, 76.3;H, 8.4; N, 4.5

EXAMPLE IV Processing of Polypropylene

    ______________________________________                                        Base formulation                                                              ______________________________________                                        Polypropylene*  100          parts                                            Calcium Stearate                                                                              0.10         part                                             ______________________________________                                         *Profax 6501 from Himont U.S.A.                                          

Stabilizers are solvent blended into polypropylene as solutions inmethylene chloride and after removal of solvent by evaporation atreduced pressure, the resin is extruded using the following extruderconditions:

    ______________________________________                                                    Temperature (°C.)                                          ______________________________________                                        Cylinder #1   232                                                             Cylinder #2   246                                                             Cylinder #3   260                                                             Gate #1       260                                                             Gate #2       260                                                             Gate #3       260                                                             RPM           100                                                             ______________________________________                                    

During extrusion, the internal extruder pressure is determined using apressure transducer. After each of the first, third and fifthextrusions, resin pellets are compression molded into 125 mil (3.2 mm)thick plaques at 193° C. and specimen yellowness index (Y.I) determinedaccording to ASTM D1925-63T.

The melt flow rate (MFR) is determined by ASTM method 1238 condition L.The melt flow rate varies inversely as the transducer pressure and bothare a measure of the molecular weight for a specific type of polymer.The results are shown in the following tables.

    ______________________________________                                                     Extrusion Temperature 260° C.                                          YI Color                                                                      After Extrusion                                                  Additives      1          3      5                                            ______________________________________                                        Base Resin     4.4        6.6    8.0                                          0.1% Antioxidant A                                                                           7.1        11.0   12.0                                         0.1% Antioxidant A +                                                                         4.1        5.7    6.1                                          0.05% Ex. I                                                                   ______________________________________                                                 Extrusion Temp. (260° C.)                                                             MFR (g/10 min)                                                 YI Color       MFR (g/10 min)                                                 After Extrusion                                                                              After Extrusion                                       Additives  1       3       5      1     5                                     ______________________________________                                        Base Resin 2.5     3.5     4.7    6.3   14.9                                  0.1% Antioxidant                                                                         7.4     13.2    15.9   3.4   6.9                                   0.1% Antioxidant                                                                         2.1     3.8     6.5    2.6   4.0                                   A + 0.05% Ex. II                                                              ______________________________________                                         Antioxidant A  Neopentyl tetrakis[3(3'5di-tert-butyl-4hydroxyphenyl)          propanoate                                                               

These data thus indicate the efective color improving properties andprocess stabilization characteristics of the instant compounds.

Summarizing, it is seen than this invention provides organic materialsstabilized against degradation by the presence therein of varioushydroxylamine derivatives as well as certain of said hydroxylaminederivatives. Variations may be made in proportions, procedures andmaterials without departing from the scope of the invention as definedby the following claims.

What is claimed is:
 1. A composition of matter comprising an organicmaterial subject to oxidative, thermal and actinic degradationstabilized with an effective stabilizing amount of a compound of theformula ##STR3## wherein R₁ is hydrogen, alkyl of 1 to 36 carbon atoms,cycloalky of 5 to 12 carbon atoms, aralkyl of 7 to 9 carbon atoms ofsaid aralkyl substituted by alkyl of 1 to 36 carbon atoms or --OR₃,wherein R₃ is hydrogen, alkyl of 1 to 36 carbon atoms, cycloalkyl of 5to 12 carbon atoms, aralkyl or 7 to 9 carbon atoms or said aralkylsubstituted by alkyl of 1 to 36 carbon atoms;n is 2-4; R₂, when n is 2,is alkylene of 2 to 12 carbon atoms, alkylidene of 2 to 6 carbon atoms,cycloalkylene of 6 to 19 carbon atoms, arylene of 6 to 10 carbon atomsor alkylearylenealkylene of 8 to 10 carbon atoms; R₂, when n is 3, isalkanetriyl of 3 to 6 carbon atoms; and R₂, when n is 4, isalkanetetrayl of 4 to 6 carbon atoms.
 2. The composition of claim 1,wherein R₁ is alkyl of 1 to 18 carbon atoms, cycloalkyl of 5 to 6 carbonatoms, benzyl, α-methyl benzyl or α,α-dimethylbenzyl.
 3. The compositionof claim 1, wherein R₁ is ##STR4## and R₃ is alkyl of 1 to 18 carbonatoms, cycloalkyl of 5 to 6 carbon atoms, benzyl, α-methylbenzyl orα,α-dimethylbenzyl.
 4. The composition of claim 1, wherein n is
 2. 5.The composition of claim 4, wherein R₂ is alkylene of 2 to 12 carbonatoms, ethylidene, cyclohexylene, phenylene or xylylene.
 6. Thecomposition of claim 5, wherein said compound is1,12-bis[4-(N-benzylhydroxyiminomethyl)phenoxy]dodecane.
 7. Thecomposition of claim 1, wherein the organic material is a syntheticpolymer.
 8. The composition of claim 7, wherein the synthetic polymer isa polyolefin polymer or copolymer.
 9. The composition of claim 8 whichalso contains a metal salt of a higher fatty acid.
 10. The compositionof claim 1 which also contains a phenolic antioxidant.
 11. Thecomposition of claim 9 which also contains a phenolic antioxidant. 12.The composition of claim 10, wherein said phenolic antioxidant isselected from the group consisting of n-octadecyl3,5-di-tert-butyl-4-hydroxyhydrocinnamate,neopentanetetrayltetrakis-(3,5-di-tert-butyl-4-hydroxyl-hydrocinnamate),di-n-octadecyl 3,5-di-tert-butyl-4-hydroxy-benzyl-phosphonate,1,3,5-tris(3,5-di-tert-butyl -4-hydroxybenzyl)isocyanurate,thiodiethylene bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamate),1,3,5-tri-methyl -2,4,6-tris(3,5-di-tert-butyl-4-hydroxy-benzyl)benzene, 3,6-di-oxaocta-methylenebis(3-methyl-5-tert-butyl -4-hydroxyhydro-cinnamate),2,6-di-tert-butyl-p-cresol,2,2'-ethylidene-bis(4,6-di-tert-butylphenol),1,3,5-tris(2,6-di-methyl-4-tert-butyl-3-hydroxybenzyl)isocyanurate,1,1,3-tris-(2-methyl-4-hydroxy-5-tert-butyl-phenyl) butane,1,3,5-tris-[2-(3,5-di-tert-butyl-4-hydroxy-hydro-cinnamoyl-oxy)-ethyl]-isocyanurate, 3,5-di-(3,5-di-tert-butyl-4-hydroxybenzyl)-mesitol, hexamethylene bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamate),1-(3,5-di-tert-butyl-4-hydroxyanilino) -3,5-di(octylthio)-s-triazine,N,N'-hexamethylene-bis(3,5di-tert-butyl-4-hydroxyhydro-cinnamamide),calcium bis(ethyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate),ethylene bis[3,3-di(3-tert-butyl- 4-hydroxyphenyl) butyrate], octyl,3,5-di-tert-butyl-4-hydroxybenzylmercaptoacetate,bis(3,5di-tert-butyl-4-hydroxyhydrocinnamoyl) hydrazide, andN,N'-bis[2-(3,5-tert-butyl-4-hydroxyhydroxo-cinnamoyloxy)ethyl]-oxamide.
 13. The composition of claim 12, wherein said phenolicantioxidant is neopentanetetrayltetrakis(3,5-di-tert-butyl-4-hydroxyhydrocinnamate), n-octadecyl3,5-di-tert-butyl- 4-hydroxyhydrocinnamate, 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl,benzene,1,3,5-tris-(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate,2,6-di-tert-butyl-p-cresol or2,2'-ethylidene-bis-(4,6di-tert-butylphenol).
 14. A method forstabilizing an organic material against oxidative, thermal and actinicdegradation which comprises stabilizing amount of a compound of claim 7.15. A composition of matter comprising a polyolefin homo- or copolymersubject to oxidative, thermal and actinic degradation stabilized with aneffective stabilizing amount of a compound of the formula ##STR5##wherein R₁ is hydrogen, alkyl of 1 to 36 carbon atoms, cycloalkyl of 5to 12 carbon atoms, aralkyl of 7 to 9 carbon atoms or said aralkylsubstituted by alkyl of 1 to 36 carbon atoms or --OR₃, wherein R₃ ishydrogen, alkyl of 1 to 36 carbon atoms, cycloalkyl of 5 to 12 carbonatoms, aralkyl of 7 to 9 carbon atoms or said aralkyl substituted byalkyl of 1 to 36 carbon atoms; andR₂ is hydrogen, alkyl of 1 to 36carbon atoms, cycloalkyl of 5 to 12 carbon atoms, aralkyl of 7 to 9carbon atoms, or said aralkyl substituted by alkyl of 1 to 36 carbonatoms.
 16. The composition of claim 15, wherein R₁ is ##STR6## and R₃ isalkyl of 1 to 18 carbon atoms, cycloalkyl of 5 to 6 carbon atoms,benzyl, α-methylbenzyl or α,α-dimethylbenzyl.
 17. The composition ofclaim 15, which also contains a phenolic antioxidant.
 18. Thecomposition of claim 17, which also contains a metal salt of a higherfatty acid.
 19. The composition of claim 15, wherein R₂ is alkyl of 1 to18 carbon atoms, cycloalkyl of 5 to 6 carbon atoms, benzyl,α-methylbenzyl or α,α-dimethylbenzyl.
 20. The composition of claim 16,wherein n is 1 and R₂ is identical to R₃.
 21. The composition of claim20, wherein said composition is N,N-bis-[p-methoxybenzyl]hydroxylamine.22. The composition of claim 20, wherein said compound isN,N-bis-[p-octadecyloxybenzyl]hydroxylamine.
 23. A compound of theformula ##STR7## wherein R₁ is hydrogen, alkyl of 1 to 36 carbon atoms,cycloalkyl of 5 to 12 carbon atoms, aralkyl of 7 to 9 carbon atoms orsaid aralkyl substituted by alkyl of 1 to 36 carbon atoms or --OR₃,wherein R₃ is hydrogen, alkyl of 1 to 36 carbon atoms, cycloalkyl of 5to 12 carbon atoms, aralkyl of 7 to 9 carbon atoms or said aralkylsubstituted by alkyl of 1 to 36 carbon atoms;m is 2-4; R₂, when m is 2,is alkylene of 2 to 12 carbon atoms, alkylidene of 2 to 6 carbon atoms,cycloalkylene of 6 to 10 carbon atoms, arylene of 6 to 10 carbon atomsor alkylenearylenealkylene of 8 to 10 carbon atoms; R₂, when m is 3, isalkanetriyl of 3 to 6 carbon atoms; and R₂, when m is 4, isalkanetetrayl of 4 to 6 carbon atoms.
 24. The compound of claim 23,wherein R₁ is alkyl of 1 to 18 carbon atoms, cycloalkyl of 5 to 6 carbonatoms, benzyl, α-methyl benzyl or α,α-dimethylbenzyl.
 25. The compoundof claim 23, wherein R₁ is ##STR8## and R₃ is alkyl of 1 to 18 carbonatoms, cycloalkyl of 5 to 6 carbon atoms, benzyl, α-methylbenzyl orα,α-dimethylbenzyl.
 26. The compound of claim 23, wherein is m is
 2. 27.The compound of claim 26, wherein R₂ is alkylene of 2 to 12 carbonatoms, ethylidene, cyclohexylene, phenylene or xylylene. 28.1,12-Bis[4-(N-benzylhydroxyiminomethyl)phenoxy]-dodecane according toclaim 27.